Olefin-Based Polymer

ABSTRACT

An olefin-based polymer and method of making the same is disclosed herein. In some embodiments, the olefin-based polymer has multiple crystallinity and satisfies the following: (1) two or more peaks in a temperature range of −20° C. to 120° C. when measured by cross-fractionation chromatography (CFC), and T(90)−T(50)&lt;8.0° C., (2) a soluble fraction (SF) of 1 wt % or less at −20° C. in CFC, (3) 15° C.&lt;elution temperature (Te)&lt;50° C., and Te has a linear correlation with a density (d) of the polymer, and satisfies the following Equation 1, Te=1,220×d−A, wherein 1,031≤A≤1,039. The olefin-based polymer according to the present invention is an olefin-based polymer having relatively increased the ratio of high crystal regions, and exhibits excellent mechanical properties such as improved tensile strength, tear strength, and flexural modulus.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a national phase entry under U.S.C. § 371 ofInternational Application No. PCT/KR2020/002479, filed on Feb. 20, 2020,which claims priority from Korean Patent Application No.10-2019-0019892, filed on Feb. 20, 2019, the entire contents of whichare incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to an olefin-based polymer, andspecifically, to a low-density olefin-based polymer prepared using twotypes of transition metal compound catalysts, which has a multiplecrystallinity and a low Melting Index.

BACKGROUND ART

Polyolefins are widely used for extrusion-molded articles, blow-moldedarticles and injection-molded articles due to excellent moldability,heat resistance, mechanical properties, hygienic quality, water vaporpermeability and appearance characteristics of molded articles thereof.However, polyolefins, particularly polyethylene, have a problem of lowcompatibility with polar resins such as nylon because of the absence ofpolar groups in the molecule, and low adhesiveness to polar resins andmetals. As a result, it is difficult to blend the polyolefin with polarresins or metals, or to laminate the polyolefin with these materials.Further, a molded article of a polyolefin has a problem of low surfacehydrophilicity and a low antistatic property.

In order to solve such a problem and to increase the affinity for apolar material, a method of grafting a polar group-containing monomeronto a polyolefin through radical polymerization has been widely used.However, this method has a problem in that cross-linking in themolecules of the polyolefin and cleavage of molecular chains occurduring the grafting reaction, and the viscosity balance of a graftpolymer and a polar resin is poor, and thus miscibility is low. There isalso a problem in that the appearance characteristics of a moldedarticle are low due to a gel component generated by intramolecularcrosslinking or a foreign substance generated by cleavage of molecularchains.

Further, as a method of preparing an olefin polymer such as an ethylenehomopolymer, an ethylene/α-olefin copolymer, a propylene homopolymer ora propylene/α-olefin copolymer, a method of copolymerizing a polarmonomer in the presence of a metal catalyst such as a titanium catalystor a vanadium catalyst was used. However, when the above-described metalcatalyst is used to copolymerize a polar monomer, there is a problemthat the molecular weight distribution or composition distribution iswide, and polymerization activity is low.

As another method, a method of polymerizing in the presence of ametallocene catalyst including a transition metal compound such aszircononocene dichloride and an organoaluminum oxy compound(aluminoxane) is known. When a metallocene catalyst is used, ahigh-molecular weight olefin polymer is obtained with high activity, andthe resulting olefin polymer has a narrow molecular weight distributionand a narrow composition distribution.

Further, as a method of preparing a polyolefin containing a polar groupusing a metallocene compound having a ligand of a non-crosslinkedcyclopentadienyl group, a crosslinked or non-crosslinked bisindenylgroup, or an ethylene crosslinked unsubstituted indenyl/fluorenyl groupas a catalyst, a method using a metallocene catalyst is also known.However, these methods have a disadvantage in that polymerizationactivity is very low. For this reason, a method of protecting a polargroup by a protecting group is carried out, but there is a problem thatthe process becomes complicated since a protecting group should beremoved again after the reaction when the protecting group isintroduced.

An ansa-metallocene compound is an organometallic compound containingtwo ligands connected to each other by a bridge group, in which therotation of the ligand is prevented and the activity and structure ofthe metal center are determined by the bridge group.

The ansa-metallocene compound is used as a catalyst in the preparationof olefin-based homopolymers or copolymers. In particular, it is knownthat an ansa-metallocene compound containing acyclopentadienyl-fluorenyl ligand can prepare a high-molecular weightpolyethylene, thereby controlling the microstructure of thepolypropylene.

Further, it is also known that an ansa-metallocene compound containingan indenyl ligand can produce a polyolefin having excellent activity andimproved stereoregularity.

As described above, various studies have been made on ansa-metallocenecompounds capable of controlling the microstructure of olefin-basedpolymers and having higher activity, but the research is stillinsufficient.

DISCLOSURE Technical Problem

An object of the present invention is to provide a low-densityolefin-based polymer prepared using two types of transition metalcompound catalysts, which has a multiple crystallinity and a low MeltingIndex, and exhibits improved mechanical properties.

Technical Solution

In order to accomplish the object, the present invention provides anolefin-based polymer having multiple crystallinity and satisfies: (1)two peaks in a temperature range of −20° C. to 120° C. when measured bycross-fractionation chromatography (CFC), wherein the two peaks excludea soluble fraction (SF) at −20° C., and T(90)−T(50)<8.0° C., where T(90)is a temperature at which 90 wt % of the olefin-based polymer is eluted,and T(50) is a temperature at which 50 wt % of the olefin-based polymeris eluted; (2) 10 wt % or less of the SF at −20° C. in CFC; (3) 15°C.<elution temperature(Te)<50° C.; and (4) Te has a linear correlationwith the density of the polymer, and satisfies the following Equation 1,

Te=1,220×density−A  [Equation 1]

wherein 1,031≤A≤1,039.

Advantageous Effects

The olefin-based polymer according to the present invention is alow-density olefin-based polymer having relatively increased the ratioof high crystal regions, and exhibits excellent mechanical propertiessuch as improved tensile strength, tear strength, and flexural modulus.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph shows CFC elution curves of Example 1 and ComparativeExample 1.

FIG. 2 is a graph shows a correlation between the density and theelution temperature (Te) of Examples 1 to 5 and Comparative Examples 1to 4.

FIG. 3 is a graph shows gel permeation chromatography (GPC) moleculardistribution curves of Example 1 and Comparative Example 1.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail toassist in the understanding of the present invention.

Terminology used in the specification and claims should not be construedas limited to conventional or literal meanings, and should be construedas having meanings and concepts corresponding to the technical idea ofthe present invention based on the principle that the inventor cansuitably define the concept of a term to explain his own invention inthe most preferable way.

In the specification, the term “a polymer” denotes a polymer compoundprepared by the polymerization of monomers having the same or differenttypes. The general term “the polymer” includes “a hybrid polymer” aswell as “a homopolymer,” “a copolymer” and “a terpolymer.” Further, “thehybrid polymer” denotes a polymer prepared by the polymerization of atleast two different types of monomers. The general term “the hybridpolymer” denotes “the copolymer” (commonly used for denoting a polymerprepared using two different types of monomers) and “the terpolymer”(commonly used for denoting a polymer prepared using three differenttypes of monomers). “The hybrid polymer” includes a polymer prepared bythe polymerization of at least four different types of monomers.

An olefin-based polymer according to the present invention has multiplecrystallinity and satisfies the following conditions of (1) to (4):

(1) two peaks in a temperature range of −20° C. to 120° C. when measuredby cross-fractionation chromatography (CFC), wherein the two peaksexclude a soluble fraction (SF) at −20° C., and T(90)−T(50)<8.0° C.,where T(90) is a temperature at which 90 wt % of the olefin-basedpolymer is eluted, and T(50) is a temperature at which 50 wt % of theolefin-based polymer is eluted;

(2) 10 wt % or less of the SF at −20° C. in CFC;

(3) 15° C.<elution temperature (Te)<50° C.; and

(4) Te has a linear correlation with the density of the polymer, andsatisfies the following Equation 1.

Te=1,220×density−A  [Equation 1]

wherein 1,031≤A≤1,039.

(1) two peaks excluding the soluble fraction (SF, Soluble Fraction) at−20° C. in a temperature range of −20° C. to 120° C. when measured bycross-fractionation chromatography (CFC), wherein the two peaks excludea soluble fraction (SF) at −20° C., and T(90)−T(50)<8.0° C.

wherein T(90) is a temperature at which 90 wt % of the olefin-basedpolymer is eluted, and T(50) is a temperature at which 50 wt % of theolefin-based polymer is eluted.

An olefin-based polymer according to the present invention has two peaksin a temperature range of −20° C. to 120° C. when taking measurements ofcross-fractionation chromatography (CFC), and satisfies that T(90)−T(50)is less than 8° C., which is the difference between T(90) and T(50),wherein T(90) is a temperature at which 90 wt % of the olefin-basedpolymer is eluted, and T(50) is a temperature at which 50 wt % of theolefin-based polymer is eluted. Specifically, T(90)−T(50) is less than7.8° C., more specifically, T(90)−T(50) is 1° C. to 7.8° C., even morespecifically, T(90)−T(50) is 5° C. to 7.8° C.

In the present invention, CFC may be measured by using a CFC machine ofPolymerChar Co. and particularly, may be measured while elevating thetemperature from −20° C. to 120° C. using o-dichlorobenzene as asolvent.

Generally, if two or more kinds of olefin-based polymers with differentdensity and crystallinity are respectively prepared in separatereactors, and then blended, two peaks may be shown when takingmeasurements of temperature rising elution fraction (TREF) or CFC of thecomposition thus mixed or the olefin block copolymer thereof. On theother hand, in the present invention, crystallinity distribution iscontrolled widely by a continuous solution polymerization in a singlereactor, and two peaks are shown when taking measurements of TREF or CFCin a state where a block is not formed in a polymer, and T(90)−T(50)satisfies the above value, resulting a small difference.

The olefin-based polymer according to an embodiment of the presentinvention may have T(90) of 20° C. or more, particularly, 20° C. to 60°C., more particularly, 25° C. to 40° C. when taking measurements of TREFor CFC. In addition, the olefin-based polymer according to an embodimentof the present invention may have T(50) of less than 40° C.,particularly, 35° C. or less, more particularly, 15° C. to 35° C. whentaking measurements of TREF.

In addition, in the present invention, T(50) means the temperature at apoint where the elution of 50 wt % of the total elution amount isterminated in a TREF or CFC elution graph expressed by an elution amountwith respect to temperature (dC/dT), and T(90) means the temperature ata point where the elution of 90 wt % of the total elution amount isterminated in a CFC elution graph expressed by an elution amount withrespect to temperature (dC/dT), and T(90)−T(50) is the differencebetween T(90) and T(50).

(2) a soluble fraction (SF) of 10 wt % or less at −20° C. incross-fractionation chromatography (CFC)

Further, the olefin-based polymer according to the present invention mayhave (2) a soluble fraction (SF) of 10 wt % or less, specifically, inthe range of 0.2 wt % to 5 wt %, and more specifically, in the range of0.2 wt % to 4 wt % at −20° C. in cross-fractionation chromatography(CFC).

The fractions eluted at a low temperature in the cross-fractionationchromatography (CFC) measurement have low crystallinity. In the presentspecification, the soluble fraction eluted at a temperature of −20° C.or less in the cross-fractionation chromatography (CFC) is defined as anultra-low crystalline region.

Generally, the lower the density of the polymer, the lower thecrystallinity, the ultra-low crystalline region is increased and impactstrength is improved. However, in a conventional olefin-based polymer,when the ultra-low crystallinity region exceeds a certain level,mechanical properties are deteriorated. The olefin-based polymeraccording to the present invention having a multiple crystallinestructure has a relatively increased high crystalline content byreducing the ultra-low crystalline content, and exhibits excellentmechanical properties such as improved tensile strength, tear strength,and flexural modulus.

(3) 15° C.<elution temperature (Te)<50° C.

In the present disclosure, Elution temperature (Te) denotes thetemperature at the highest point in a TREF or CFC elution graphexpressed by an elution amount with respect to temperature (dC/dT).

In addition, for calculating Te, the initiation point of each peak inthe graph of elution amount with respect to temperature (dC/dT) may bedefined as a point where the elution of a polymer is initiated based ona base line, and the end point of each peak may be defined as a pointwhere the elution of a polymer is terminated based on a base line. Whentwo peaks overlap, and the end point of the previous peak and startpoint of the following peak cannot be defined based on the base line,the point at which the peak eluting at a relatively low temperaturereaches the maximum point and then decreases and then begins to increaseagain is defined as the end point of the previous peak and the startpoint of the following peak. In addition, a peak expressed in −20° C. to−10° C. may be regarded as a portion of a peak expressed in after −10°C., which is shown in this position due to the limitation ofmeasurement. Accordingly, the peak expressed in this position may beincluded and treated as a peak expressed in after −10° C.

In the present disclosure, a single crystallinity denotes having onepeak excluding the soluble fraction (SF, Soluble Fraction) at −20° C.,and a multiple crystallinity denotes having two or more peaks excludingthe soluble fraction (SF, Soluble Fraction) at −20° C. in a elutiongraph expressed by an elution amount with respect to temperature(dC/dT). In addition, in the present disclosure, when the polymer has amultiple crystallinity, Elution temperature (Te) is the temperature atthe highest point in a CFC elution graph expressed by an elution amountwith respect to temperature (dC/dT), that is, only the peak of thelarger peak is used as Te.

The olefin-based polymer according to the present invention satisfies15° C.<elution temperature (Te)<50° C., and specifically, may satisfy15° C.≤Te≤40° C., and more specifically, 20° C.≤Te≤40° C.

(4) Te has a linear correlation with the density of the polymer, andsatisfies the following Equation 1.

Te has a linear correlation with the density of the polymer, andsatisfies the following Equation 1:

Te=1,220×density−A  [Equation 1]

In Equation 1, A satisfies in a range of 1,031≤A≤1,039.

The olefin-based polymer according to the present invention may furthersatisfy (5) a density (d) of 0.860 g/cc to 0.890 g/cc when measured inaccordance with ASTM D-792, specifically, 0.865 g/cc to 0.890 g/cc, andmore specifically, 0.865 g/cc to 0.880 g/cc.

In addition, the olefin-based polymer according to the present inventionmay further satisfy (6) a melt index (MI, 190° C., 2.16 kg loadconditions) of 0.1 dg/min to 10.0 dg/min, specifically, 0.1 dg/min to8.0 dg/min, and more specifically, 0.1 dg/min to 5.0 dg/min.

The melting index (MI) may be controlled by adjusting the amount used ofa catalyst during a polymerization process, and may influence amechanical properties, impact strength and moldability of anolefin-based polymer.

In addition, the olefin-based polymer according to the present inventionmay further satisfy (7) a weight average molecular weight (Mw) of 70,000g/mol to 500,000 g/mol, specifically, 70,000 g/mol to 300,000 g/mol, andmore specifically, 70,000 g/mol to 200,000 g/mol.

Further, the olefin-based polymer according to an embodiment of thepresent invention may satisfy (8) a molecular weight distribution (MWD),which is a ratio (Mw/Mn) of a weight average molecular weight (Mw) to anumber average molecular weight (Mn), in the range of 1.0 to 3.0,specifically in the range of 1.5 to 2.8, and more specifically in therange of 1.8 to 2.6. The olefin-based polymer according to an embodimentof the present invention may be polymerized using a catalyst compositionincluding two types of transition metal compounds having acharacteristic structure, thereby exhibiting a narrow molecular weightdistribution.

In addition, the olefin-based polymer according to an embodiment of thepresent invention has one monomodal-type peak in a molecular weightdistribution curve. The olefin-based polymer of the present invention ispolymerized using a catalyst composition containing two types oftransition metal compounds, and as a result, has the molecular weightdistribution of single distribution, while having multiplecrystallinity.

Generally, the density of the olefin-based polymer is affected by thetype and content of the monomers used in the polymerization, the degreeof polymerization and the like, and the copolymer is affected by thecontent of the comonomer. The olefin-based polymer of the presentinvention is polymerized using a catalyst composition containing twotypes of transition metal compounds having a characteristic structure,and a large amount of comonomers may be introduced, and the olefin-basedpolymer of the present invention has a low density in the range asdescribed above.

The olefin-based polymer may have (9) a melt temperature (Tm) of 100° C.or less, specifically of 80° C. or less, and more specifically in therange of 10° C. to 70° C. obtained in a differential scanningcalorimetry (DSC) curve obtained by DSC measurement.

The olefin-based polymer is a homopolymer of any one selected from anolefin-based monomer, specifically, an alpha-olefin-based monomer, acyclic olefin-based monomer, a diene olefin-based monomer, a trieneolefin-based monomer, and a styrene-based monomer, or a copolymer of twoor more selected them. More specifically, the olefin-based polymer maybe a copolymer of ethylene and an alpha-olefin having 3 to 12 carbonatoms or 3 to 10 carbon atoms, even more specifically, a copolymer ofethylene and 1-octene.

The alpha-olefin comonomer may include any one or a mixture of two ormore selected from the group consisting of propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene,norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene,vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene,1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and3-chloromethyl styrene.

More specifically, the olefin copolymer according to an embodiment ofthe present invention may be a copolymer of ethylene and propylene,ethylene and 1-butene, ethylene and 1-hexene, ethylene and4-methyl-1-pentene or ethylene and 1-octene, and more specifically, theolefin copolymer according to an embodiment of the present invention maybe a copolymer of ethylene and 1-octene.

When the olefin-based polymer is a copolymer of ethylene and analpha-olefin, the amount of the alpha-olefin may be 90 wt % or less,more specifically 70 wt % or less, still more specifically in the rangeof 5 wt % to 60 wt % and even more specifically in the range of 20 wt %to 50 wt % with respect to the total weight of the copolymer. When thealpha-olefin is included in the above-described range, it is easy torealize the above-mentioned physical properties.

The olefin-based polymer according to an embodiment of the presentinvention, which has the above-described physical properties andconstitutional characteristics may be prepared by a continuous solutionpolymerization reaction in the presence of a metallocene catalystcomposition including at least one type of a transition metal compoundin a single reactor. Accordingly, in the olefin-based polymer accordingto an embodiment of the present invention, a block formed by linearlyconnecting two or more repeating units derived from one monomer amongmonomers constituting a polymer in the polymer is not formed. That is,the olefin-based polymer according to the present invention does notinclude a block copolymer, but may be selected from the group consistingof a random copolymer, an alternating copolymer and a graft copolymer,more particularly, may be a random copolymer.

Specifically, the olefin-based copolymer of the present invention may beobtained by a preparation method including a step of polymerizingolefin-based monomers in the presence of a catalyst composition forolefin polymerization including a transition metal compound representedby the following Formula 1 and a transition metal compound representedby the following Formula 2 in an molar ratio of 1:5 to 1:10,specifically, of 1:5 to 1:7.

However, in the preparation of an olefin-based polymer according to anembodiment of the present invention, the structure ranges of the firsttransition metal compound and the second transition metal compound arenot limited to specifically disclosed types, and all modifications,equivalents, or replacements included in the scope and technical rangeof the present invention should be understood to be included in thepresent invention.

In Formula 1,

R₁ may be the same or different, and each independently representhydrogen, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to20 carbon atoms, an aryl, a silyl, an alkylaryl, an arylalkyl or ametalloid radical of a Group 4 metal substituted with a hydrocarbyl, andthe two R₁ may be connected together by alkylidene radicals including analkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20carbon atoms to form a ring;

R₂ may be the same or different, and each independently representhydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; an aryl; analkoxy; an aryloxy; or an amido radical, and two or more of the R₂ maybe connected to each other to form an aliphatic ring or an aromaticring;

R₃ may be the same or different, and each independently representhydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; or analiphatic or aromatic ring which contains nitrogen and is substitutedwith an aryl radical or unsubstituted, and when the number ofsubstituents is plural, two or more substituents among the substituentsmay be connected to each other to form an aliphatic or aromatic ring;

M₁ is a Group 4 transition metal;

Q₁ and Q₂ each independently represent a halogen; an alkyl having 1 to20 carbon atoms; an alkenyl; an aryl; an alkylaryl; an arylalkyl; analkylamido having 1 to 20 carbon atoms; an arylamido; or an alkylideneradical having 1 to 20 carbon atoms;

In Formula 2,

R₄ may be the same or different, and each independently representhydrogen, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to20 carbon atoms, an aryl, a silyl, an alkylaryl, an arylalkyl or ametalloid radical of a Group 4 metal substituted with a hydrocarbyl, andthe two R₄ may be connected together by alkylidene radicals including analkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20carbon atoms to form a ring;

R₅ may be the same or different, and each independently representhydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; an aryl; analkoxy; an aryloxy; or an amido radical, and two or more of the R₅ maybe connected to each other to form an aliphatic ring or an aromaticring;

R₆ may be the same or different, and each independently representhydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; or analiphatic or aromatic ring which contains nitrogen and is substitutedwith an aryl radical or unsubstituted, and when the number ofsubstituents is plural, two or more substituents among the substituentsmay be connected to each other to form an aliphatic or aromatic ring;

M₂ is a Group 4 transition metal;

Q₃ and Q₄ each independently represent a halogen; an alkyl having 1 to20 carbon atoms; an alkenyl; an aryl; an alkylaryl; an arylalkyl; analkylamido having 1 to 20 carbon atoms; an arylamido; or an alkylideneradical having 1 to 20 carbon atoms.

Further, in another embodiment of the present invention, in Formula 1,R₁ and R₂ may be the same or different, and each independently mayrepresent hydrogen; an alkyl having 1 to 20 carbon atoms; an aryl; or asilyl,

R₃ may be the same or different, and may be an alkyl having 1 to 20carbon atoms; an alkenyl having 2 to 20 carbon atoms; an aryl; analkylaryl; an arylalkyl; an alkoxy having 1 to 20 carbon atoms; anaryloxy; or an amido; and two or more adjacent R₃ among the R₃ may beconnected to each other to form an aliphatic or aromatic ring;

Q₁ and Q₂ may be the same or different, and each may independentlyrepresent a halogen; an alkyl having 1 to 20 carbon atoms; an alkylamidohaving 1 to 20 carbon atoms; or an arylamido,

M₁ may be a Group 4 transition metal.

Further, in Formula 2, R₄ and R₅ may be the same or different, and eachmay independently represent hydrogen; an alkyl having 1 to 20 carbonatoms; an aryl; or a silyl,

R₆ may be the same or different, and may be an alkyl having 1 to 20carbon atoms; an alkenyl having 2 to 20 carbon atoms; an aryl; analkylaryl; an arylalkyl; an alkoxy having 1 to 20 carbon atoms; anaryloxy; or an amido; and two or more R₆ among the R₆ may be connectedto each other to form an aliphatic or aromatic ring;

Q₃ and Q₄ may be the same or different, and each may independentlyrepresent a halogen; an alkyl having 1 to 20 carbon atoms; an alkylamidohaving 1 to 20 carbon atoms; or an arylamido,

M₂ may be a Group 4 transition metal.

Further, in the transition metal compound represented by Formula 1 orFormula 2, a metal site is connected by a cyclopentadienyl ligand towhich tetrahydroquinoline is introduced, and the structure thereof has anarrow Cp-M-N angle and a wide Q₁-M-Q₂ (Q₃-M-Q₄) angle to which amonomer approaches. In addition, Cp, tetrahydroquinoline, nitrogen andthe metal site are connected in order via the bonding of a ring shape toform a more stable and rigid pentagonal ring structure. Therefore, whenthese compounds are activated by reacting with a cocatalyst such asmethylaluminoxane or B(C₆F₅)₃ and then applied to olefin polymerization,an olefin-based polymer having characteristics such as high activity,high molecular weight, high copolymerization properties and the like maybe polymerized even at a high polymerization temperature.

Each of the substituents defined in the present specification will bedescribed in detail as follows.

In the present specification, unless particularly defined otherwise, ahydrocarbyl group means a monovalent hydrocarbon group having 1 to 20carbon atoms formed only with carbon and hydrogen regardless of itsstructure such as an alkyl group, an aryl group, an alkenyl group, analkinyl group, a cycloalkyl group, an alkylaryl group and an arylalkylgroup.

The term “halogen” used in the present specification, unless otherwisespecified, refers to fluorine, chlorine, bromine and iodine.

The term “alkyl” used in the present specification, unless otherwisespecified, refers to a linear or branched hydrocarbon residue.

The term “alkenyl” used in the present specification, unless otherwisespecified, refers to a linear or branched alkenyl group.

The branched chain may be an alkyl having 1 to 20 carbon atoms; analkenyl having 2 to 20 carbon atoms; an aryl having 6 to 20 carbonatoms; an alkylaryl having 7 to 20 carbon atoms; or an arylalkyl having7 to 20 carbon atoms.

According to an embodiment of the present invention, the aryl grouppreferably has 6 to 20 carbon atoms, and specifically includes phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like,but is not limited thereto.

The alkylaryl group refers to an aryl group substituted with the alkylgroup.

The arylalkyl group refers to an alkyl group substituted with the arylgroup.

The ring (or a heterocyclic group) refers to a monovalent aliphatic oraromatic hydrocarbon group which has ring atoms with 5 to 20 carbonatoms and contains one or more heteroatoms, and may be a single ring ora condensed ring of two or more rings. Further, the heterocyclic groupmay be unsubstituted or substituted with an alkyl group. Examplesthereof include indoline, tetrahydroquinoline and the like, but thepresent invention is not limited thereto.

The alkylamino group refers to an amino group substituted with the alkylgroup, and includes a dimethylamino group, a diethylamino group and thelike, but is not limited thereto.

According to an embodiment of the present invention, the aryl grouppreferably has 6 to 20 carbon atoms, and specifically includes phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like,but is not limited thereto.

The compound of Formula 1 may be one or more selected from the groupconsisting of the following Formulae 1-1 and 1-2, and the compound ofFormula 2 may be the following Formula 2-1, but the present invention isnot limited thereto.

In addition, it may be a compound having various structures within theranges defined in Formulae 1 and 2.

The transition metal compound of Formula 1 and the transition metalcompound of Formula 2 allow introduction of a large amount of analpha-olefin as well as low-density polyethylene due to the structuralcharacteristics of the catalyst, and thus it is possible to prepare alow-density polyolefin copolymer having a density in the range of 0.850g/cc to 0.865 g/cc. Further, when the transition metal compound ofFormula 1 and the transition metal compound of Formula 2 are usedtogether in an molar ratio of 1:1 to 1:5, and specifically of 1:1 to1:4, an olefin-based polymer having a high molecular weight, a narrowmolecular weight distribution, a low density and a low hardness may beprepared.

For example, the transition metal compounds of Formulae 1 and 2 may beprepared by the following method.

In Reaction Scheme 1, R₁ to R₃, M₁, Q₁ and Q₂ each are as defined inFormula 1.

Further, the transition metal compound of Formula 2 may be prepared bythe following method as an example.

In Reaction Scheme 2, R₄ to R₆, M₂, Q₃ and Q₄ each are as defined inFormula 2.

Formulae 1 and 2 may be prepared according to the method described in KRPatent Application Laid-Open No. 2007-0003071, and the entire contentsof which are incorporated herein by reference.

The transition metal compound of Formula 1 and the transition metalcompound of Formula 2 may be used alone or in combination including oneor more cocatalyst compounds represented by the following Formula 3,Formula 4 and Formula 5 in addition to the transition metal compound ofFormula 1 and the transition metal compound of Formula 2 as a catalystfor the polymerization reaction.

—[Al(R₇)—O]_(a)—  [Formula 3]

A(R₇)₃  [Formula 4]

[L-H]⁺[W(D)₄]⁻ or [L]⁺[W(D)₄]⁻  [Formula 5]

In Formulae 3 to 5,

R₇ may be the same or different, and are each independently selectedfrom the group consisting of a halogen, a hydrocarbyl having 1 to 20carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms substitutedwith a halogen,

A is aluminum or boron,

D each independently represents an aryl having 6 to 20 carbon atoms oran alkyl having 1 to 20 carbon atoms in which at least one hydrogen atommay be substituted with a substituent selected from the group consistingof a halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxyhaving 1 to 20 carbon atoms and an aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis acid,

W is a Group 13 element, and

a is an integer of 2 or more.

Examples of the compound represented by Formula 3 includealkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane,isobutylaluminoxane, butylaluminoxane and the like, and modified alkylaluminoxanes having two or more of the alkylaluminoxanes mixed therein,and specifically may be methyl aluminoxane and modified methylaluminoxane (MMAO).

Examples of the compound represented by Formula 4 includetrimethylaluminum, triethylaluminum, triisobutylaluminum,tripropylaluminum, tributylaluminum, dimethylchloroaluminum,tri-iso-propyl aluminum, tri-sec-butyl aluminum, tricyclopentylaluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum,trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum,triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide,dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutylboron, tripropyl boron, tributyl boron and the like, and specifically,may be selected from trimethyl aluminum, triethyl aluminum andtriisobutyl aluminum.

Examples of the compound represented by Formula 5 includetriethylammonium tetraphenylboron, tributylammonium tetraphenylboron,trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron,trimethylammonium tetra(p-tolyl) boron, trimethylammoniumtetra(o,p-dimethylphenyl) boron, tributylammoniumtetra(p-trifluoromethylphenyl) boron, trimethylammoniumtetra(p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron,N,N-diethylanilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron,trimethylphosphonium tetraphenylboron, dimethylaniliniumtetrakis(pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenyl aluminum, trimethylammoniumtetraphenyl aluminum, tripropylammonium tetraphenyl aluminum,trimethylammonium tetra(p-tolyl) aluminum, tripropylammoniumtetra(p-tolyl) aluminum, triethylammoniumtetra (o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl) aluminum,trimethylammonium tetra(p-trifluoromethylphenyl) aluminum,tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylaniliniumtetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenyl aluminum,triphenylphosphonium tetraphenyl aluminum, trimethylphosphoniumtetraphenyl aluminum, tripropylammonium tetra(p-tolyl) boron,triethylammonium tetra(o,p-dimethylphenyl) boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) boron, triphenylcarboniumtetrapentafluorophenylboron and the like.

The catalyst composition may be prepared by a method including the stepsof 1) bringing a primary mixture of a transition metal compoundrepresented by Formula 1 and a transition metal compound represented byFormula 2 into contact with a compound represented by Formula 3 or 4 toobtain a mixture; and 2) adding a compound represented by Formula 5 tothe mixture, as the first method.

Further, the catalyst composition may be prepared by a method ofbringing a transition metal compound represented by Formula 1 and atransition metal compound represented by Formula 2 into contact with acompound represented by Formula 3, as the second method.

In the first method among the above-described preparation methods of thecatalyst composition, the molar ratio of the transition metal compoundrepresented by Formula 1 and the transition metal compound representedby Formula 2/the compound represented by Formula 3 or 4 may be in therange of 1/5,000 to 1/2, specifically in the range of 1/1000 to 1/10,and more specifically in the range of 1/500 to 1/20. When the molarratio of the transition metal compound represented by Formula 1 and thetransition metal compound represented by Formula 2/the compoundrepresented by Formula 3 or 4 exceeds 1/2, the amount of the alkylatingagent is very small, and thus the alkylation of the metal compound isnot fully carried out. When the molar ratio is less than 1/5000, thealkylation of the metal compound is carried out, but the activation ofthe alkylated metal compound is not fully achieved due to the sidereaction between the remaining excess alkylating agent and theactivating agent which is a compound of Formula 5. Further, the molarratio of the transition metal compound represented by Formula 1 and thetransition metal compound represented by Formula 2/the compoundrepresented by Formula 5 may be in the range of 1/25 to 1, specificallyin the range of 1/10 to 1, and more specifically in the range of 1/5to 1. When the molar ratio of the transition metal compound representedby Formula 1 and the transition metal compound represented by Formula2/the compound represented by Formula 5 is more than 1, the amount ofthe activator is relatively small, so that the metal compound is notfully activated, and thus the activity of the resulting catalystcomposition may be lowered. When the molar ratio is less than 1/25, theactivation of the metal compound is fully performed, but the unit costof the catalyst composition may not be economical due to the remainingexcess activator, or the purity of the produced polymer may be lowered.

In the second method among the above-described preparation methods ofthe catalyst composition, the molar ratio of the transition metalcompound represented by Formula 1 and the transition metal compoundrepresented by Formula 2/the compound represented by Formula 3 may be inthe range of 1/10,000 to 1/10, and specifically in the range of 1/5000to 1/100, and more specifically in the range of 1/3000 to 1/500. Whenthe molar ratio is more than 1/10, the amount of the activator isrelatively small, so that the activation of the metal compound is notfully achieved, and thus the activity of the resulting catalystcomposition may be lowered. When the molar ratio is less than 1/10,000,the activation of the metal compound is fully performed, but the unitcost of the catalyst composition may not be economical due to theremaining excess activator, or the purity of the produced polymer may belowered.

In the preparation of the catalyst composition, a hydrocarbon-basedsolvent such as pentane, hexane, heptane or the like, or an aromaticsolvent such as benzene, toluene or the like may be used as a reactionsolvent.

Further, the catalyst composition may include the transition metalcompound and a cocatalyst compound in the form of being supported on acarrier.

The carrier may be used without any particular limitation as long as itis used as a carrier in a metallocene catalyst. Specifically, thecarrier may be silica, silica-alumina, silica-magnesia or the like, andany one or a mixture of two or more thereof may be used.

In the case where the support is silica, there are few catalystsliberated from the surface during the olefin polymerization processsince the silica carrier and the functional groups of the metallocenecompound of Formula 1 form a chemical bond. As a result, it is possibleto prevent the occurrence of fouling of the wall surface of the reactoror the polymer particles entangled with each other during thepreparation process of the olefin-based polymer. Further, theolefin-based polymer prepared in the presence of the catalyst containingthe silica carrier has an excellent particle shape and apparent densityof the polymer.

More specifically, the carrier may be high-temperature dried silica orsilica-alumina containing a siloxane group having high reactivity on thesurface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitratecomponent such as Na₂O, K₂CO₃, BaSO₄, Mg(NO₃)₂ or the like.

The polymerization reaction for polymerizing the olefin-based monomermay be carried out by a conventional process applied to thepolymerization of olefin monomers such as continuous solutionpolymerization, bulk polymerization, suspension polymerization, slurrypolymerization, emulsion polymerization or the like.

The polymerization reaction of olefin monomers may be carried out in thepresence of an inert solvent, and examples of the inert solvent includebenzene, toluene, xylene, cumene, heptane, cyclohexane,methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene and 1-octene,but the present invention is not limited thereto.

The polymerization of the olefin-based polymer may be carried out at atemperature of from about 25° C. to about 500° C. and the reactionpressure of from about 1 to 100 kgf/cm².

Specifically, the polymerization of the olefin-based polymer may becarried out at a temperature in the range of about 25° C. to about 500°C., particularly, in the range of 80° C. to 250° C., and moreparticularly in the range of 100° C. to 200° C. Further, the reactionpressure at the time of polymerization may be in the range of 1 kgf/cm²to 150 kgf/cm², preferably 1 kgf/cm² to 120 kgf/cm², and more preferably5 kgf/cm² to 100 kgf/cm².

Due to having improved physical properties, the olefin-based polymer ofthe present invention may be used for blow molding, extrusion molding orinjection molding in diverse fields and uses including wrapping,construction, daily supplies, or the like, such as a material of anautomobile, a wire, a toy, a fiber, a medicine, or the like.Particularly, the olefin-based polymer may be used for an automobilewhich requires excellent impact strength.

Further, the olefin-based polymer of the present invention may beusefully used in the production of molded articles.

The molded article may particularly include a blow molded article, aninflation molded article, a cast molded article, an extrusion laminatemolded article, an extrusion molded article, a foamed molded article, aninjection molded article, a sheet, a film, a fiber, a monofilament, anon-woven fabric, or the like.

MODE FOR CARRYING OUT THE INVENTION Examples

Hereinafter, the present invention will be explained in particular withreference to the following examples. However, the following examples areillustrated to assist the understanding of the present invention, andthe scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of Transition Metal Compound 1

(1) Preparation of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

(i) Preparation of Lithium Carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150mL) were put into a Schlenk flask. The above-described Schlenk flask wasimmersed in a low-temperature bath at −78° C. formed of dry ice andacetone, and stirred for 30 minutes. Subsequently, n-BuLi (39.3 mL, 2.5M, 98.24 mmol) was added thereto via syringe under a nitrogenatmosphere, and thereby pale yellow slurry was formed. Then, after theflask was stirred for 2 hours, the temperature of the flask was raisedto room temperature while removing the produced butane gas. The flaskwas immersed again in a low-temperature bath at −78° C. to lower atemperature, and then CO₂ gas was introduced thereto. As carbon dioxidegas was introduced, the slurry disappeared and the solution becameclear. The flask was connected to a bubbler to remove the carbon dioxidegas, and the temperature was raised to room temperature. Thereafter, anexcess amount of CO₂ gas and a solvent were removed under vacuum. Theflask was transferred to a dry box, and pentane was added thereto,followed by vigorous stirring and filtration to obtain lithium carbamatewhich is a white solid compound. The white solid compound is coordinatedwith diethyl ether. The yield is 100%.

¹H NMR (C₆D₆, C₅D₅N): δ 1.90 (t, J=7.2 Hz, 6H, ether), 1.50 (br s, 2H,quin-CH₂), 2.34 (br s, 2H, quin-CH₂), 3.25 (q, J=7.2 Hz, 4H, ether),3.87 (br s, 2H, quin-CH₂), 6.76 (br d, J=5.6 Hz, 1H, quin-CH) ppm

¹³C NMR (C₆D₆): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57,142.04, 163.09 (C═O) ppm

(ii) Preparation of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

The lithium carbamate compound prepared in Step (i) (8.47 g, 42.60 mmol)was put into a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol)and 45 mL of diethyl ether were added in sequence. The Schlenk flask wasimmersed in a low-temperature bath at −20° C. including acetone and asmall amount of dry ice and stirred for 30 minutes, and then t-BuLi(25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of thereaction mixture turned red. The mixture was stirred for 6 hours while atemperature was maintained at −20° C. A CeCl₃.2LiCl solution (129 mL,0.33 M, 42.60 mmol) dissolved in tetrahydrofuran andtetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe,and then introduced into the flask under a nitrogen atmosphere. Thetemperature of the flask was slowly raised to room temperature. After 1hour, a thermostat was removed and the temperature was maintained atroom temperature. Subsequently, water (15 mL) was added to the flask,and ethyl acetate was added thereto, followed by filtration to obtain afiltrate. The filtrate was transferred to a separatory funnel, followedby the addition of hydrochloric acid (2 N and 80 mL) and shaking for 12minutes. A saturated aqueous solution of sodium hydrogencarbonate (160mL) was added for neutralization, and then an organic layer wasextracted. Anhydrous magnesium sulfate was added to the organic layer toremove moisture, followed by filtration, and the filtrate was taken toremove the solvent. The obtained filtrate was purified by columnchromatography using hexane and ethyl acetate (v/v, 10:1) to obtainyellow oil. The yield was 40%.

¹H NMR (C₆D₆): δ 1.00 (br d, 3H, Cp-CH₃), 1.63-1.73 (m, 2H, quin-CH₂),1.80 (s, 3H, Cp-CH₃), 1.81 (s, 3H, Cp-CH₃), 1.85 (s, 3H, Cp-CH₃), 2.64(t, J=6.0 Hz, 2H, quin-CH₂), 2.84-2.90 (br, 2H, quin-CH₂), 3.06 (br s,1H, Cp-H), 3.76 (br s, 1H, N—H), 6.77 (t, J=7.2 Hz, 1H, quin-CH), 6.92(d, J=2.4 Hz, 1H, quin-CH), 6.94 (d, J=2.4 Hz, 1H, quin-CH) ppm

(2) Preparation of[(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η⁵,κ-N]titaniumdimethyl)

(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η⁵,κ-N]dilithium compound

After8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline(8.07 g, 32.0 mmol) prepared by Step (1) and 140 mL of diethyl etherwere put in a round flask in a dry box, a temperature was lowered to−30° C. and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added whilestirring. The reaction was allowed to proceed for 6 hours while thetemperature was raised to room temperature. Thereafter, the solid wasobtained by filtration while washing with diethyl ether several times. Avacuum was applied to remove the remaining solvent to obtain adi-lithium compound (9.83 g) which is a yellow solid. The yield was 95%.

¹H NMR (C₆D₆, C₅D₅N): δ 2.38 (br s, 2H, quin-CH₂), 2.53 (br s, 12H,Cp-CH₃), 3.48 (br s, 2H, quin-CH₂), 4.19 (br s, 2H, quin-CH₂), 6.77 (t,J=6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H,quin-CH) ppm

(ii) Preparation of (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η⁵,κ-N]titanium dimethyl

In a dry box, TiCl₄.DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL)were put into a round flask and MeLi (21.7 mL, 31.52 mmol and 1.4 M) wasslowly added while stirring at −30° C. After stirring for 15 minutes,[(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η⁵,κ-N]dilithiumcompound (5.30 g, 15.76 mmol) prepared in Step (i) was put into theflask. The mixture was stirred for 3 hours while the temperature wasraised to room temperature. After completion of the reaction, thesolvent was removed by vacuum, the mixture was dissolved in pentane andfiltered to obtain the filtrate. A vacuum was applied to remove pentaneto obtain a dark brown compound (3.70 g). The yield was 71.3%.

¹H NMR (C₆D₆): δ 0.59 (s, 6H, Ti—CH₃), 1.66 (s, 6H, Cp-CH₃), 1.69 (br t,J=6.4 Hz, 2H, quin-CH₂), 2.05 (s, 6H, Cp-CH₃), 2.47 (t, J=6.0 Hz, 2H,quin-CH₂), 4.53 (m, 2H, quin-CH₂), 6.84 (t, J=7.2 Hz, 1H, quin-CH), 6.93(d, J=7.6 Hz, quin-CH), 7.01 (d, J=6.8 Hz, quin-CH) ppm

¹³C NMR (C₆D₆): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96,120.95, 126.99, 128.73, 131.67, 136.21 ppm

Preparation Example 2: Preparation of Transition Metal Compound 2

(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl) indoline wasprepared in the same manner as in (1) of Preparation Example 1 exceptthat 2-methylindoline was used instead of 1,2,3,4-tetrahydroquinoline in(1)(i) of Preparation Example 1. The yield was 19%.

¹H NMR (C₆D₆): δ 6.97 (d, J=7.2 Hz, 1H, CH), δ 6.78 (d, J=8 Hz, 1H, CH),δ 6.67 (t, J=7.4 Hz, 1H, CH), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (brs, 1H, NH), δ 3.24-3.08 (m, 2H, quinoline-CH₂, Cp-CH), δ 2.65 (m, 1H,quinoline-CH₂), δ 1.89 (s, 3H, Cp-CH₃), δ 1.84 (s, 3H, Cp-CH₃), δ 1.82(s, 3H, Cp-CH₃), δ 1.13 (d, J=6 Hz, 3H, quinoline-CH₃), δ 0.93 (3H,Cp-CH₃) ppm.

(2) Preparation of[(2-methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titaniumdimethyl)

(i) A di-lithium salt compound (compound 4g) in which 0.58 equivalent ofdiethyl ether was coordinated was obtained (1.37 g, 50%) in the samemanner as in (2)(i) of Preparation Example 1 except that2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g,8.88 mmol) was used instead of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline.

¹H NMR (Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6 Hz, 1H, CH),δ 6.32 (t, 1H, CH), δ 4.61 (brs, 1H, CH), δ 3.54 (m, 1H, CH), δ 3.00 (m,1H, CH), δ 2.35-2.12 (m, 13H, CH, Cp-CH₃), δ 1.39 (d, indoline-CH₃) ppm.

(ii) A titanium compound was prepared in the same manner as in (2) (ii)of Preparation Example 1 using the di-lithium salt compound (compound4g) (1.37 g, 4.44 mmol) prepared in the above (i).

¹H NMR (C₆D₆): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4 Hz, 1H, CH), δ4.96 (m, 1H, CH), δ 2.88 (m, 1H, CH), δ 2.40 (m, 1H, CH), δ 2.02 (s, 3H,Cp-CH₃), δ 2.01 (s, 3H, Cp-CH₃), δ 1.70 (s, 3H, Cp-CH₃), δ 1.69 (s, 3H,Cp-CH₃), δ 1.65 (d, J=6.4 Hz, 3H, indoline-CH₃), δ 0.71 (d, J=10 Hz, 6H,TiMe₂-CH₃) ppm.

Example 1

A 1.5 L-continuous process reactor was filled with a hexane solvent (7kg/h) and 1-octene (1.15 kg/h), and a temperature at the top of thereactor was preheated to 150° C. A triisobutyl aluminum compound (0.06mmol/min), a mixture (0.53 μmol/min) of a transition metal compoundobtained by mixing the transition metal compound 1 obtained inPreparation Example 1 and the transition metal compound 2 obtained inPreparation Example 2 in a molar ratio of 1:5, and a dimethylaniliniumtetrakis(pentafluorophenyl) borate cocatalyst (1.59 μmol/min) weresimultaneously introduced into the reactor. Subsequently, ethylene (0.87kg/h) was then fed into the reactor, and the copolymerization reactionwas continued at 150° C. for 30 minutes or more in a continuous processat a pressure of 89 bar to obtain a copolymer. After drying for morethan 12 hours in a vacuum oven, the physical properties were measured.

Examples 2 to 5

The copolymerization reaction was carried out by using the same methodas in Example 1 to obtain a copolymer except that the reactiontemperature and the amount of the reaction material were changed asshown in the following Table 1.

Comparative Example 1

EG8150 manufactured by the Dow Chemical Company was purchased and used.

Comparative Example 2

The copolymerization reaction was carried out by using the same methodas in Example 1 to obtain a copolymer except that only the transitionmetal compound 2 was used as a catalyst.

Comparative Examples 3 and 4

The copolymerization reaction was carried out using the two transitionmetal catalysts as in Example 1. The ratio of the two transition metals,the ratio of the catalyst to the cocatalyst, the reaction temperatureand the amount of the comonomer were changed as shown in the followingTable 1. The reaction proceeded to obtain a copolymer.

TABLE 1 Catalyst ratio (Transition metal Catalyst Cocatalyst TiBAlReaction on compound (μmol/ (μmol/ (mmol/ Ethylene 1-octene temperature1:2) min) min) min) (kg/h) (kg/h) (° C.) Example 1 1:5 0.53 1.59 0.060.87 7.0 150 Example 2 1:5 0.53 1.59 0.06 0.87 7.0 146 Example 3 1:50.70 2.10 0.06 0.87 7.0 150 Example 4 1:5 0.43 1.50 0.06 0.87 7.0 146Example 5 1:5 0.73 1.59 0.06 0.87 7.0 150 Comparative 0:1 0.7 2.1 0.090.87 7.0 149 Example 2 Comparative 1.4:1   0.3 0.9 0.05 0.87 7.0 148Example 3 Comparative 1:3 0.42 1.26 0.05 0.87 7.0 149 Example 4

Experimental Example 1

The physical properties of the copolymers of Examples 1 to 5 andComparative Examples 1 to 4 were evaluated according to the followingmethods, and the results are shown in the following Table 2.

1) Soluble Fraction, Te (Elution Temperature), T(90), T(50)

The measurement equipment was a CFC of Polymer Char. First, a solutionof the copolymer was fully dissolved in an oven at 130° C. for 60minutes in a CFC analyzer using o-dichlorobenzene as a solvent, pouredinto a TREF column adjusted to 135° C., and then cooled to 95° C. andstabilized for 45 minutes. Subsequently, the temperature of the TREFcolumn was lowered to −20° C. at a rate of 0.5° C./min, and thenmaintained at −20° C. for 10 minutes. Thereafter, the elution amount(mass %) was measured using an infrared spectrophotometer. Subsequently,the operation of raising the temperature of the TREF column to apredetermined temperature at a rate of 20° C./min and maintaining atemperature reached for a predetermined time (i.e., about 27 minutes)was repeated until the temperature of the TREF column reached 130° C.,and the amount of eluted fraction (mass %) was measured during eachtemperature range.

The content of the ultra-low crystalline region means the content of thefraction eluted at −20° C. or less, and the elution temperature wasmeasured the temperature at the highest point in peak.

2) Density of Polymer

Measurement was performed in accordance with ASTM D-792.

3) Melt Index (MI) of Polymer

Measurement was performed in accordance with ASTM D-1238 [condition E,190° C. and a load of 2.16 kg].

4) Weight Average Molecular Weight (Mw, g/Mol) and Molecular WeightDistribution (MWD)

The number-average molecular weight (Mn) and the weight-averagemolecular weight (Mw) each were measured by gel permeationchromatography (GPC), and the molecular weight distribution wascalculated by dividing the weight average molecular weight by the numberaverage molecular weight.

Column: PL Olexis

Solvent: Trichlorobenzene (TCB)

Flow rate: 1.0 ml/min

Concentration of specimen: 1.0 mg/ml

Injection amount: 200 μl

Column temperature: 160° C.

Detector: Agilent High Temperature RI detector

Standard: Polystyrene (Calibration using cubic function)

5) Melting Point (Tm) of Polymer

The melting point was obtained using the differential scanningcalorimeter (DSC) 6000 manufactured by PerkinElmer. That is, after thetemperature was increased to 200° C., the temperature was maintained atthat temperature for 1 minute, then decreased to −100° C., and thetemperature was increased again to obtain the top of the DSC curve asthe melting point. At this time, the rate of temperature rise and fallis 10° C./min, and the melting point is obtained during the secondtemperature rise.

6) Measurement of Comonomer Content

50 mg of a specimen was taken and put in a vial, 1 ml of a TCE-d2solvent was added thereto, and the specimen was completely dissolvedusing a heat gun and was transferred to a NMR tube. 1H NMR was measuredwith number of scan (ns)=2048 (3 h 30 min), and measurement temperatureof 393K. In order to remove 1-octene or 1-butene which may remain in thespecimen, a polymer was reprecipitated and prepared prior to conductingthe NMR analysis. In detail, 1 g of the polymer was completely dissolvedin chloroform at 70° C., and the polymer solution thus obtained wasslowly poured into 300 ml of methanol while stirring to re-precipitatethe polymer. The re-precipitated polymer was dried in vacuum at roomtemperature. The above-described process was repeated one more to obtaina polymer from which 1-octene and 1-butene were removed.

50 mg of the specimen of the polymer thus obtained was dissolved in 1 mlof TCE-d2 solvent. Measurement was conducted with an acquisition time ofthree seconds and a pulse angle of 30° for 2048 times at roomtemperature using a Bruker AVANCEIII 500 MHz NMR equipment. Thecomonomer content was calculated using integration values of ethylene,1-butene and 1-octene peaks in a region of 0.5-1.5 ppm. The number ofdouble bonds was calculated based on the integration value of doublebonds in a region of 4.5-6.0 ppm. Macromolecules 2014, 47, 3782-3790 wasreferred to.

TABLE 2 GPC Density MI_(2.16) Mw peak Tm % (g/mL) (dg/min) (g/mol) MWDcount (° C.) [1-C8] Example 1 0.871 0.44 135098 2.35 1 56.6 34.1 Example2 0.870 0.28 140790 2.33 1 56.1 35.3 Example 3 0.866 1.23 112341 2.29 151.0 39.0 Example 4 0.868 0.12 156116 2.33 1 53.6 37.0 Example 5 0.8743.6  90391 2.32 1 61.4 31.6 Comparative 0.869 0.47 138442 2.18 1 60.135.7 Example 1 Comparative 0.868 0.54 128563 2.33 1 50.3 36.0 Example 2Comparative 0.870 0.50 126936 2.31 1 54.5 32.1 Example 3 Comparative0.870 0.52 128420 2.30 1 54.7 32.1 Example 4

TABLE 3 CFC peak Crystal Te SF T (90) T (50) T (90)- count structure (°C.) (%) (° C.) (° C.) T (50) Example 1 2 multiple 28.5 0.7 34.5 27.0 7.5crystallinity Example 2 2 multiple 27.1 1.3 33.5 26.0 7.5 crystallinityExample 3 2 multiple 22.2 3.1 28.0 21.5 6.5 crystallinity Example 4 2multiple 25.1 1.9 32.0 25.0 7.0 crystallinity Example 5 2 multiple 32.10.3 36.5 30.5 6.0 crystallinity Comparative 1 Single 29.3 1.0 34.5 25.09.5 Example 1 crystallinity Comparative 1 Single 19.9 0.3 28.5 19.5 9.0Example 2 crystallinity Comparative 2 multiple 14.4 0.7 38.0 21.0 17Example 3 crystallinity Comparative 2 multiple 27.4 1.1 34.5 25.0 9.5Example 4 crystallinity

In addition, FIG. 1 is a graph shows CFC elution curves of Example 1 andComparative Example 1, and FIG. 2 is a graph shows a correlation betweenthe density and the Te (elution temperature) of Examples 1 to 5 andComparative Examples 1 to 4. Referring to FIG. 1, Example 1 has twopeaks in the CFC elution curve, and the width of the peak is narrowerthan that of Comparative Example 1. Since the width of the peak isnarrow, as can be seen in Table 2, T(90)−T(50) is less than 8 in theExample, unlike the Comparative Example. In addition, referring to Table1 and FIG. 2, a density and Te (elution temperature) have a linearcorrelation, and the correlation satisfy the Equation 1. However,Comparative Examples 1 to 3 do not satisfy the Equation 1, andComparative Example 4 satisfies the Equation 1, but T(90)−T(50) is 8 ormore.

In addition, FIG. 3 is a graph shows GPC molecular distribution curvesof Example 1 and Comparative Example 1. Example 1 and ComparativeExample 1 have one single peak. Referring to FIG. 1 and FIG. 2, thecomparative examples have a single molecular weight distribution and asingle crystalline distribution, whereas the examples have a singlemolecular weight distribution and a multiple crystalline distribution.

Experimental Example 2

Specimens of olefin-based polymer prepared in Examples 1, andComparative Examples 1 to 4 were prepared by injection molding at atemperature of 200° C. using an injection machine, and the specimensthus prepared were stood in a room with a constant temperature andconstant humidity for one day. Then, tensile strength, tear strength,and flexural modulus were measured and are shown in Table 3 below.

1) Tensile Strength and Tear Strength of Olefin-Based Polymer

The tensile strength and tear strength were measured according to ASTMD638 using the INSTRON 3365.

2) Flexural Modulus of Olefin-Based Polymer

The flexural modulus (Secant 1%) was measured according to ASTM D790using the INSTRON 3365.

3) Hardness (Shore A) of Olefin-Based Polymer

Hardness was measured according to ASTM D2240 using GC610 STAND forDurometer of TECLOCK Co. and a Shore hardness tester Type A of MitutoyoCo.

TABLE 4 Tensile Tear Flexural Hardness Density MI_(2.16) Tm strengthstrength modulus (Shore (g/mL) (dg/min) (° C.) MWD (MPa) (kN/m) (MPa) A)Example 1 0.871 0.44 56.6 2.35 11.73 270. .67 14.6 70.4 Comparative0.869 0.47 60.1 2.24 11.45 24.85 12.0 67.74 Example 1 Comparative 0.8680.54 50.3 2.33 9.00 23.45 12.2 66.76 Example 2 Comparative 0.870 0.5054.5 2.31 9.98 24.06 12.44 69.61 Example 3 Comparative 0.870 0.52 54.72.30 10.46 23.81 13.752 68.83 Example 4

Referring to Table 4, it can be seen that Example 1 has improved tensilestrength, tear strength, flexural modulus, and hardness compared toComparative Examples 1 to 4 having similar density and MI.

1. An olefin-based polymer having multiple crystallinity and satisfyingthe following: (1) two peaks in a temperature range of −20° C. to 120°C. when measured by cross-fractionation chromatography (CFC), whereinthe two peaks exclude a soluble fraction (SF) at −20° C., andT(90)−T(50)<8.0° C., wherein T(90) is a temperature at which 90 wt % ofthe olefin-based polymer is eluted, and T(50) is a temperature at which50 wt % of the olefin-based polymer is eluted; (2) 10 wt % or less ofthe SF at −20° C. in CFC; (3) 15° C.<Te<50° C., wherein elutiontemperature (Te) is a temperature at which a maximum in elution amountwith respect to temperature (dC/dT) occurs in CFC; and (4) Te has alinear correlation with a density (d) of the polymer, and satisfies thefollowing Equation 1,Te=1,220×d−A  [Equation 1] wherein 1,031≤A≤1,039.
 2. The olefin-basedpolymer according to claim 1, wherein the olefin-based polymer has adensity (d) ranging from 0.860 to 0.890 g/cc.
 3. The olefin-basedpolymer according to claim 1, wherein the olefin-based polymer has adensity (d) ranging from 0.865 to 0.880 g/cc.
 4. The olefin-basedpolymer according to claim 1, wherein the olefin-based polymer has amelt index (MI, 190° C., 2.16 kg load) ranging from 0.1 g/10 min to 10.0g/10 min.
 5. The olefin-based polymer according to claim 1, wherein theolefin-based polymer has a weight average molecular weight (Mw) in arange of 70,000 to 500,000.
 6. The olefin-based polymer according toclaim 1, wherein the olefin-based polymer has a molecular weightdistribution (MWD) in a range of 1.0 to 3.0.
 7. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer has a melttemperature (Tm) of 100° C. or less, wherein Tm is measured bydifferential scanning calorimetry (DSC).
 8. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer is a copolymerpolymerized from ethylene and an alpha-olefin comonomer having 3 to 12carbon atoms.
 9. The olefin-based polymer according to claim 8, whereinthe alpha-olefin comonomer includes any one selected from the groupconsisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene,ethylidene norbornene, phenyl norbornene, vinyl norbornene,dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene,styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene,or a mixture of at least two thereof.
 10. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer is a copolymerpolymerized from ethylene and 1-octene.
 11. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer has a singlemolecular weight distribution defined by having one peak when measuredby gel permeation chromatography (GPC).
 12. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer is prepared by amethod comprising: polymerizing an olefin-based monomer in the presenceof a catalyst composition, wherein the catalyst composition includes atransition metal compound represented by the following Formula 1 and atransition metal compound represented by the following Formula 2 in anmolar ratio of 1:5 to 1:7:

wherein, in Formula 1, each R₁ are the same or different, and areindependently hydrogen, an alkyl having 1 to 20 carbon atoms, an alkenylhaving 2 to 20 carbon atoms, an aryl, a silyl, an alkylaryl, anarylalkyl, or a metalloid radical of a Group 4 metal substituted with ahydrocarbyl, and the two R₁ are capable of being connected together byalkylidene radicals including an alkyl having 1 to 20 carbon atoms or anaryl radical having 6 to 20 carbon atoms to form a ring, each R₂ are thesame or different, and are independently hydrogen, a halogen, an alkylhaving 1 to 20 carbon atoms, an aryl, an alkoxy, an aryloxy, or an amidoradical, and the two R₂ are capable of being connected to each other toform an aliphatic ring or an aromatic ring, each R₃ are the same ordifferent, and are independently hydrogen, a halogen, an alkyl having 1to 20 carbon atoms, or an aliphatic or aromatic ring which containsnitrogen and is substituted with an aryl radical or unsubstituted, andwhen the number of substituents is plural, two or more substituentsamong the substituents are capable of being connected to each other toform an aliphatic or aromatic ring, M₁ is a Group 4 transition metal,and Q₁ and Q₂ are each independently a halogen, an alkyl having 1 to 20carbon atoms, an alkenyl, an aryl, an arylalkyl, an alkylamido having 1to 20 carbon atoms, an arylamido, or an alkylidene radical having 1 to20 carbon atoms,

wherein, in Formula 2, each R₄ are the same or different, and areindependently hydrogen, an alkyl having 1 to 20 carbon atoms, an alkenylhaving 2 to 20 carbon atoms, an aryl, a silyl, an alkylaryl, anarylalkyl, or a metalloid radical of a Group 4 metal substituted with ahydrocarbyl, and the two R₄ are capable of being connected together byalkylidene radicals including an alkyl having 1 to 20 carbon atoms or anaryl radical having 6 to 20 carbon atoms to form a ring, each R₅ are thesame or different, and are independently hydrogen, a halogen, an alkylhaving 1 to 20 carbon atoms, an alkoxy, an aryloxy, or an amido radical,and the two R₅ are capable of being connected to each other to form analiphatic ring or an aromatic ring, each R₆ are the same or different,and are independently hydrogen, a halogen, an alkyl having 1 to 20carbon atoms, or an aliphatic or aromatic ring which contains nitrogenand is substituted with an aryl radical or unsubstituted, and when thenumber of substituents is plural, two or more substituents among thesubstituents are capable of being connected to each other to form analiphatic or aromatic ring, M₂ is a Group 4 transition metal, and Q₃ andQ₄ are each independently a halogen, an alkyl having 1 to 20 carbonatoms, an alkenyl, an aryl, an alkylaryl, an arylalkyl, an alkylamidohaving 1 to 20 carbon atoms, an arylamido, an alkylidene radical having1 to 20 carbon atoms.
 13. The olefin-based polymer according to claim12, wherein the olefin-based polymer is prepared by a continuoussolution polymerization reaction using a continuous stirred tank reactorin the presence of the catalyst composition.